Azo dye from substituted anilides of 2.3 hydroxynaphthoic acid



P atentecl A ug. 1 6, 1 932 UNITED STATES PATENT OFFICE ERNEST IE. GRE'I'HZER AND LINDLEY E. MILLS, 0F MIDLAND, MICHIGAN, ASSIGNORS TO THE DOW CHEMICAL COMPANY, OF MICHIGAN MIDLAND, MICHIGAN, A CORPORATION OF AZO DYE FROM SUBSTITUTED ANILIDES or 2.3 YnRoxyNATHTnoIo ACID" j 1 No Drawing. Application filed June 8,

droxynaphthoic acid is coupled'with a diazotized arylamine, but distinguished from azo dyes hitherto known in that the aforesaid aryli e component thereof is formed by condensing said acid with an aromatic amine having probably the general formula;

on o ONH-X wherein X represents a halogen group, R represents an alkyl, aryl, di-aryl,0r aralkoxy radical, and R represents an aryl radical of the benzene or naphthalene-series.

In our pending application, Serial No. 537,504, filed May 14, 1931, and entitled Substituted anilides of 2.3-hydroxynaphthoic acid, we have described the preparation and properties of the several arylides from which the azo dyes hereinafter described are prepared. It is well known that azo dyes fast to light and washing are produced by coupling arylides of 2.3-hydroxynaphthoic acid with diazotized or tetrazotized arylamines. o have discovered, however, that when mono-alkoxy-di-halo-anilides or mono-aryloxy di halo anilides of 2.3 hydroxynaphthoic acid are so coupled the dyestuffs formed thereby are fast toward light and washing and the colors produced are deep and clear in tone. The invention, then, consists of azo dyestuffs derived from mono-alkoXy-di-haloanilides and mono-aryloxy-di-halo-analides of 2.3-hydroxynaphthoic acid, together with 1931. Serial N0. 543,010.

methods for the preparation thereof, as here-.

inafterj fully described and particularly 7 produced in substance per se or deposited upon suitable substrata to form lakes, in which forms they are useful pigments because of their insolubility, stability, and fastness.

Substituted anilines'from which the aryl-- ides hereinafter utilized were made, were themselves prepared in the following way Para-dichlorobenzene was chlorinated to obtain trichlorobenzene and the latter nitrated to the corresponding trichloro-mononitro-benzene of melting point 57C., and having probably the formula OzN Mono methoxy dichloro nitrobenzene,

having a-melting point of approximately 7 4 I C. and-having probably the formula or v OzN ture of 2025 C. for a period of 16 hours.

The reaction mixture was then poured into 400 cc. of water, the resulting mixture filtered, and the residue recrystallized from methyl alcohol. Theproduct has a melting point of approximately 749 0. Upon analysis,our, product was found tocontain practically-the theoretical quantity of chlorine. The yield of crude product was practically theoretical.

Mono-ethoxy-dichloro-nitrobenzene ing probably the formula;

hav-

AlQzHl was prepared in the following H A solution consisting of 27 grains (0.1 mole) of tri-chloro-nitrobenzene, and 4 grams (0.1 mole) of sodium hydroxide dissolved in 150 cc. of absolute ethyl alcohol was permitted tostandi'or a period of from 10 to 12 hours and at a temperature-oi from 25-30 The reaction mixture was then poured into 400 cc. of water and the resulting mixture :filtered, washed and dried. There'was obtained thereby, 23.5 grams of material melting at 5054 G. Recrystal lization from methyl alcohol raised the melting point to 61 CI The product was analyzed and foundto contain the theoretical quantity of chlorine.-

Mono phenoxy dichloro nitrobenzene having probably the formula O zN was prepared in the following way A solution consisting :of 8.4 grams (0.2

mole.) of .9 5 :per: centpure sodium hydroxide,

10 cc. .dfgwn'en andlQO cc; .of pheno l was heated untilall. wateams removedv and the temperature of the issuing vapor was that of the boiling point of pure phenol. The flask was then cooled. and 200 cc. of toluene added in order to prevent over-heating during subsequent treatment oi thereaction mixture. After the addition of toluene, 45.8 grams (0.2 mole) of trichloro-nitrobenzene was -added and the=mixture::refluxed gently for aperiochof 2 hours The reaction mixture was thencooled poured into waterland The mono-alkoxy-dichloro-anilines product obtained consisted of light yellow crystals having a melting point of approxi- 'mately 120.5 G. The yield was practically 89 per cent theoretical.

-' and mono-aryloxy dichloro-anilines used in preparing the'arylides from which the azo dyes selves prepared by reducing the above described nitro compounds in the following way In a3-liter, .3-neck flash fitted with. an; oil seal stirrer and reflux condenser were placed 400 grains of iron-filings, 200 cc. of water."

50 cc. of ethyl alcohol and 2 cc. of glacial acetic acid. The mixture was stirred and refluxed for one-half hour, 0.25 of a gram molecular: weight of the nitro compound being added in small quantities during this ,period. Stirring and refluxing were continued-for from 4: to 16 hours, then 2 to 8 grams of sodium carbonate and 300 cc. of

benzene added 'to the mixture. -A.fter stirring for an additional one-half hour, the

benzene layer was separated, the aqueous layer filtered and the filtrateagain extracted with a 300 cc. portion of benzene. The combined benzene extracts were then treated with an excess of concentrated hydrochloric acid. The hydrochloride of the amine precipitated either imniediatelyor uponstanding and was filtered from the mixture and washed with benzene. The yield was usually about per cent theoretical. From the previously mentioned nitrocompounds the following amines were prepared in the manner described; mono-methoxy-dichloro-aniline having a meltingpoint of approximately 58 C., 'mono ethoxy-dichloroeaniline, which was found to -be liquid at room tem- V hereinafter described were made were them-x peratnre, mono phenoxy dichloro aniline ,having a; meltingpoint of approximately "84 C. and mono-orthophenylphenoxy=dichloro-f aniline having-- amelting point of approxrmatelylOl. C;

Apreferred manner inwhich azo dyestuffs comprising the inventio ijmay 'beprepared is I.

illustrated in the specific. examples given be.-

low, it being understoochhowever, that such examples are not to be construed as a limitation upon the invention Ewample 1 The mono-niethoxy-dichloro-anilide of 2.3- hydroxynaphthoic acid is prepared by heating equimolecular quantities of mono-methoxy-dicliloro-aniline and 2.3-hydroxynaph- .thoic acid in the presence of approximately I 13 per cent oftheir combined weight (slightly more than one-third of a molecular equivalent) of phosphorus trichloride under reflux and with stirring and in thepresence of sufficient toluene to permit such stirring,

for a periodof from?) to 5 hours. An excess of sodium carbonate over that required to neutralize the acid'present' is then added and the toluene removed by distilling with steam. The aqueous residue containing the anilide product in suspension therein is fil- 1 tered and the precipitate is then purified by dissolving-indilute, l to 2 per cent, caustic alkaligsolution, preferably in the presence of alcohol, filtering from unreacted monomethoxy-dichloro-aniline, and precipitating by acidification of the alkaline solution. The intermediate compound so produced has probably the formula;

Cl Q CONH- 01 V 0 OH: Cotton material is impregnated with a slightly alkaline solution of the above arylide to which may be added advantageously, but not necessarily, formaldehyde and a fixative, such as Turkey red oil or an aluminum salt. The material is then dipped in a'cold solution of sodium acetate or carbonate, and the dye developed by adding a diazo solution derived from 3-amino-4-methoxy-dipheny1. The color developed is a clear, dark cardinal. The dyestuff has probably the formula;

By procedure similar to that described in Example 1, the mono-ethoxy-dichloro-anilide of 2.3-hydroxynaphthoic acid was prepared by condensing mono-ethoxy-dichloro-aniline with 2.3-hydroxynaphthoic acid. The dye was developed by adding a diazo solution from 3.4-dichloro-aniline. The color developed was a Castilian red. The dyestufi' has probably the formula;

602E; E trample 3 The mono-phenoxydichloro-anilide of 2.3- hydroxynaphtlioic acid was prepared by condensing mono-phenoxy-dichloro-aniline with 63 2.3-hydroxynaphthoic acid in a way similar to that described in Example 1. The dye was developed by treatment with a diazo. solution from 2-phenyll-nitro-aniline.1 The color developed was scarlet. The dyestuff" has probably the formula;

' Example 4 The .mono-orthophenylphehOxy-dichloro anilide of 2.3hydroxynaphthoic acid, having probably the formula;

OH A c1 CONHQ-Ol was prepared by condensing mono-orthophenylphenoxy-dich'loro-aniline with 2.3-hydroxynaphthoic acid in a manner similar to that described in Example 1. The dye was developed by treatment with a diazo solution from 3-phenyll-methoxy-aniline. The color developed was strawberry. The dyestuff has probably the formula;

0cm WV c1 @0 oNH -o1 o v 7 I In like manner, we have prepared other dyes of the same general type, for example,

those shown in the accompanying table, the

color of the dyes being designated therein lCfl according to the Standard Color Card of America, (1928 Ed.), issued by the Textile Color Card Association of the United States,

Inc.

. 4.4-dibromo-2.2-diamino-diphenyl oxide.

T ble Colors of azo dyes formed by coupling diazotized emineslwitlr t Amines diazotized and coupled with substituted anilides of 2.3-hydroxynsphthoic acid Mono methoxy dichloroanilide of 2.3 -hydroxynaphthoic acid Mono ethoxy Monophenoxy r ,dichloro-anilide dichloro-anilide of 2.3 -'hydroxyof 2.3'-hydroxynaphthoic acid naphthoic acid chloro-anilide of M-nitro-aniline Pimento Plum Alpha-plienoxy naphthylamine Dianisidi 4.4-dia1nino-diphenyl oxide Alpha-naphthy1amine 3-pheny14methoxy-aniline 2-nitro-4-methyl-aniline e 2.2-dimethoxy-3.3-dia1ni 2-methyl-5 nitro-aniline 5.S-dichloro-Lamino-naph 3-chl0ro-4'rnethoxy-ani1ine LS-diamino-naphthalene. 3-benzoylamino-aniline 4-benzoylamino-aniline Cardinal Garnet Maroon Goya Goya Egg plant 3chloro-4-phenoxy-aniline. -H; Goya -amino-naphthyl-azo-4-aniline Arnino-dinaphthyl oxido 2.4.5-tricl1loro-aniline U 4-(phenyl az0)-1-amino-napl1thalene 4-aminoazob enzene O-nitro-aniline 4-(3-nitro-phenyl.1-azo)- -s\m1no-naphthalene.

Scarlet Scarlet Midnight Castilian red Homage blue Burgundy Oastilian red Raspberry Castilian red Dark cardinal Dark cardinal Navy blue E gg plant Dark cardinal Paprica ,Tangerine Indian orange Goya Paprica Tangerine Scarlet Castilianred Weigelia Paprica Geranium Prune Purple Maroon" Homage blue Ensign blue Purple navy Cardinal Cardinal v Castilian red Raspberry Oastilian red Harvard crims0n 'CaStlllflH red Midnight blue Raspberry blue er the dye is applied by developing on the fiber or prepared in substance for, use as a pigment. Mordanting or other auxiliary treatments for promoting the absorption of the dye by the fiber, or after treatment with metallic salts, "e. g. chromium, copper, or aluminum salts, for fixing the dye or modifying its color tone may be optionally employed without departing from the spirit of our invention. I

In the following claims it is understood that the invention comprehends the coupling of the herein described arylides of 2.3-hydroxynaphthoic acid with any diazotized aromatic mono-, di-, or poly-aminov compound, as well as the azo dyestufls derived therefrom. Other modes of applying the'principle of our invention maybe employed instead of the one explained, change being made as regards the method or materials employed, provided the steps or compounds stated by any of the following claims or the equivalent of such stated steps or compounds be employed. We therefore particularly pointout and distinctly claim as our invention 1. In a method of making'an azo dyestuif, the step which consists in coupling an arylide of 2.3-hy'droirynaphthoic acid having the gen eral formula;

wherein X represents a halogen group, and wherein R represents a, radical selected from the group consisting of alkyl radicals and aryl radicals of the benzene and diphenyl series, with a diazotized aromatic amino compound.

2. In a method of making'an azo dyestuf'f, the step which consists in coupling an arylide of 2.3-hydroxynaphthoic acid having probably the formula;

wherein X represents a halogen'group, and whereinR representsa radical selected from whereinR representsa radical selected from I the group'consisting of alkyl radicals and aryl 2.3 -l1ydroxy-\- naphthoic acid radicals of the benzene and diphenyl series, with a diazotized aromatic amino compound.

4. In a method of making an azo dyestufi', the step which consists in coupling an arylide. of 2.3-hydroxynaphthoic acid having probably the formula;

OCH:

with a diazotized aromatic amino compound- 5. In a method of making an azo dyestulf, the step which consists in coupling an arylideof 2.3-hydroxynaphthoic acid having probably the formula;

OH oomnOm I 002115 with a diazotized aromatic amino compound.

6. In a method of making an azo dyestuff, the step which consists in coupling an arylide of 2.3-hydroxynaphthoic acid having probably the formula;

with a diazotized aromatic amino compound. 7. As a new compound, an azo dyestuff having the general formula;

R represents an aryl radical of the benzene or na hthalene series.

9. s a new compound, an azo dyestuif having probably the formula;

wherein R represents an aryl radical of the benzene 0r naphthalene series.

10. As a new compound, an azo dyestuff having probably the formula;

OH 01 -c ONE-G01 (iCzHg wherein R represents an aryl radical of the benzene or naphthalene series.

11. As a new compound, an azo dyestulf having probably the formula;

N=NR

' v p I on V CONH-QOI 0 wherein R represents an aryl radical of the benzene or naphthalene series.

Signed by us this 29th day of May, 1931. ERNEST F. GRETHER. L-INDLEY E. MILLS.

wherein X represents a halogen group, R

OH f

0 ONE X wherein X represents a halogen group, R represents a radical selected from the group consisting of alkyl radicals and aryl radicals of the benzene and diphenyl series, and

Certificate of Correction Patent No. 1,872,035. August 16,1932. ERNEST F. GRETHER ET AL.

It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 1, line 49, for the compound Word mono-aryloxy-di-halo-ana1ides read m0n0-a1-yl0wy-di-hal0-cmilides; page 2, line 77, for flash read flask; page 5, lines 55 to 61, claim 8, strike out the formula and insert instead and that the said Letters Patent should be read With these corrections therein that the same may conform to the record of the casein the Patent Ofiice.

Signed and sealed this 1st day of November, A. D. 1932.

[SEAL] M. J. MOORE,

Acting Commissioner of Patents. 

